Simplification through complexity: the role of Ni-complexes in catalysed diyne-cyclobutanone [4+2+2] cycloadditions, a comparative DFT study.
Simplification through complexity: the role of Ni-complexes in catalysed diyne-cyclobutanone [4+2+2] cycloadditions, a comparative DFT study.
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DOI：
10.1039/c2cp40067g
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发表时间：
2012-04
期刊：
影响因子：
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通讯作者：
J. Tao;D. Fang;G. Chass
中科院分区：
文献类型：
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作者：
J. Tao;D. Fang;G. Chass
对镍（（0））催化的二炔-环丁酮[4+2+2]环加成反应进行了一系列密度泛函理论（DFT）实验，定量证实了所提出的多步反应机理，同时阐明了镍在反应中的催化作用. Ni催化过程的几何和能量结果与一步非催化补充进行了比较。结果表明，第一氧化是速率决定步骤，与分子内反应是两个竞争途径的首选之一。配体的身份也被证明大大影响反应障碍，导致产品收率的大偏差，与实验观察直接一致。
A series of density functional theory (DFT) experiments carried out on selected nickel((0))-catalysed diyne-cyclobutanone [4+2+2] cycloadditions provided quantitative confirmation of proposed multistep mechanisms, while clarifying the catalytic role of Ni in the reactions. Geometric and energetic results of the Ni-catalysed process were compared to the one-step non-catalysed complement. Results show the first oxidation to be the rate-determining step, with the intramolecular reaction being the preferred one of the two competing pathways. Ligand-identity is also shown to greatly influence reaction barriers, leading to large deviation in product yields, in direct agreement with experimental observations.